Anion-exchange chromatographic separation of Hg for isotope ratio measurements by multicollector ICPMS

A procedure is described for precise Hg isotope ratio measurements by solution nebulization multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). Hg was released from geological samples using aqua regia extraction and then separated from other matrix elements with the aid of anion-exchange chromatography using strongly basic Dowex 1-X8 anion-exchange resin. Performance of the chromatographic procedure was evaluated using various types of replacement anions for elution of mercury, including l-cysteine, thiourea, NO3-, and SO42-. A solution of 0.15% l-cysteine in 0.06 M HCl was found to be the most convenient eluent for subsequent MC-ICPMS measurements. The optimized procedure provides separation of Hg from virtually all concomitant matrix elements while maintaining quantitative (>95%) recovery. In addition, band displacement chromatographic experiments were conducted to assess whether the anion-exchange purification can produce Hg isotope fractionation artifacts. No isotope fractionation between the Hg(II)-l-cysteine complex in aqueous solution and Hg ions in the anion-exchange resin was observed. Hg isotope ratio measurements were performed using the bracketing standards approach and on-line correction for instrumental mass discrimination using Tl spiking and normalization to the 205Tl/203Tl ratio. The absence of spectral interference during Hg isotope ratio measurements was verified using a three-isotope plot. Uncertainties of Hg isotope ratio measurements for replication of the entire procedure, expressed as two standard deviations, are better than +/-0.08 per thousand/amu. The described procedure facilitates study of variations in the isotopic composition of Hg in nature.     

Fe isotope variations in natural materials measured using high mass resolution multiple collector ICPMS

We present the first measurements of Fe isotope variations in chemically purified natural samples using high mass resolution multiple-collector inductively coupled plasma source mass spectrometry (MC-ICPMS). High mass resolution allows polyatomic interferences at Fe masses to be resolved (especially, (40)Ar(14)N(+), (40)Ar(16)O(+), and (40)Ar(16)OH(+)). Simultaneous detection of Fe isotope ion beams using multiple Faraday collectors facilitates high-precision isotope ratio measurements. Fe in basalt and paleosol samples was extracted and purified using a simple, single-stage anion chemistry procedure. A Cu "element spike" was used as an internal standard to correct for variations in mass bias. Using this procedure, we obtained data with an external precision of 0.03-0.11 per thousand and 0.04-0.15 per thousand for delta(56/54)Fe and delta(57/54)Fe, respectively (2sigma). Use of Cu was necessary for such reproducibility, presumably because of subtle effects of residual sample matrix on mass bias. These findings demonstrate the utility of high-resolution MC-ICPMS for high-precision Fe isotope analysis in geologic and other natural materials. They also highlight the importance of internal monitoring of mass bias, particularly when using routine methods for Fe extraction and purification.     

Lithium isotope composition of basalt glass reference material

We present data on the lithium isotope compositions of glass reference materials from the United States Geological Survey (USGS) and the National Institute of Standards and Technology (NIST) determined by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), thermal ionization mass spectrometry (TIMS), and secondary ionization mass spectrometry (SIMS). Our data on the USGS basaltic glass standards agree within 2 per thousand, independent of the sample matrix or Li concentration. For SIMS analysis, we propose use of the USGS glasses GSD-1G (delta(7)Li 31.14 +/- 0.8 per thousand, 2sigma) and BCR-2G (delta(7)Li 4.08 +/- 1.0 per thousand, 2sigma) as suitable standards that cover a wide range of Li isotope compositions. Lithium isotope measurements on the silica-rich NIST 600 glass series by MC-ICPMS and TIMS agree within 0.8 per thousand, but SIMS analyses show systematic isotopic differences. Our results suggest that SIMS Li isotope analyses have a significant matrix bias in high-silica materials. Our data are intended to serve as a reference for both microanalytical and bulk analytical techniques and to improve comparisons between Li isotope data produced by different methodologies.     

Delta34S measurements of sulfur by multicollector inductively coupled plasma mass spectrometry

An accurate and precise method for the determination of delta34S measurements by multicollector inductively coupled plasma mass spectrometry has been developed. Full uncertainty budgets, taking into consideration all the uncertainties of the measurement process, have been calculated. The technique was evaluated by comparing measured values with a range of isotopically enriched sulfur solutions prepared by gravimetric addition of a 34S spike. The gravimetric and measured results exhibited a correlation of R2 >0.999. Repeat measurements were also made after adding Na (up to 420 microg g(-1)) and Ca (up to 400 microg g(-1)) salts to the sulfur standard. No significant deviations in the delta34S values were observed. The Russell correction expression (Ingle, C.; Sharp, B.; Horstwood, M.; Parrish, R.; Lewis, D. J. J. Anal. At. Spectrom. 2003, 18, 219) was used to correct for mass bias on the 34S/32S isotope amount ratio from the mass bias observed for the 30Si/28Si isotope amount ratio. Consistent compensation for instrumental mass bias was achieved. Resolution of the measured delta34S values was better than 1 per thousand after consideration of all uncertainty components. The technique was evaluated for practical applications by measurement of delta34S for a range of mineral waters by pneumatic nebulization sample introduction and the analysis of genuine and counterfeit pharmaceuticals using both laser ablation sample introduction and liquid chromatography. For the former two cases polyatomic interferences were resolved by operating the MC-ICPMS in medium resolution, while for the chromatographic analyses polyatomic interferences were minimized by the use of a membrane desolvator, allowing the instrument to be operated at a resolution of 400.     

High precision measurements of non-mass-dependent effects in nickel isotopes in meteoritic metal via multicollector ICPMS

We measured the Ni isotopic composition of metal from a variety of meteorite groups to search for variations in the 60Ni abundance from the decay of the short-lived nuclide 60Fe (t(1/2) = 1.49 My) and for possible nucleosynthetic effects in the other stable isotopes of Ni. We developed a high-yield Ni separation procedure based on a combination of anion and cation exchange chromatography. Nickel isotopes were measured on a single-focusing, multicollector, inductively coupled mass spectrometer (MC-ICPMS). The external precision on the mass-bias-corrected 60Ni/58Ni ratio (+/-0.15 epsilon; 2sigma) is comparable to similar studies using double-focusing MC-ICPMS. We report the first high-precision data for 64Ni, the least abundant Ni isotope, obtained via MC-ICPMS. The external precision on the mass-bias-corrected 64Ni/58Ni ratio (+/-1.5 epsilon; 2sigma) is better than previous studies using thermal ionization mass spectrometry. No resolvable excesses relative to a terrestrial standard in the mass-bias-corrected 60Ni/58Ni ratio were detected in any meteoritic metal samples. However, resolvable deficits in this ratio were measured in the metal from several unequilibrated chondrites, implying a 60Fe/56Fe ratio of approximately 1 x 10(-6) at the time of Fe/Ni fractionation in chondritic metal. A 60Fe/56Fe ratio of (4.6 +/- 3.3) x 10(-7) is inferred at the time of Fe/Ni fractionation on the parent bodies of magmatic iron meteorites and pallasites. No clearly resolvable non-mass-dependent anomalies were detected in the other stable isotopes of Ni in the samples investigated here, indicating that the Ni isotopic composition in the early solar system was homogeneous (at least at the level of precision reported here) at the time of meteoritic metal formation.     

Precise and traceable (13)C/(12)C isotope amount ratios by multicollector ICPMS

A new method for the measurement of SI traceable carbon isotope amount ratios using a multicollector inductively coupled mass spectrometer (MC-ICPMS) is reported for the first time. Carbon (13)C/(12)C isotope amount ratios have been measured for four reference materials with carbon isotope amount ratios ranging from 0.010659 (delta(13)C(VPDB) = -46.6 per thousand) to 0.011601 (delta(13)C(VPDB) = +37 per thousand). Internal normalization by measuring boron (11)B/(10)B isotope amount ratios has been used to correct for the effects of instrumental mass bias. Absolute (13)C/(12)C ratios have been measured and corrected for instrumental mass bias and full uncertainty budgets have been calculated using the Kragten approach. Corrected (13)C/(12)C ratios for NIST RM8545 (Lithium Carbonate LSVEC), NIST RM8573 (L-Glutamic Acid USGS40), NIST RM8542 (IAEA-CH6 Sucrose) and NIST RM8574 (L-Glutamic Acid USGS41) differed from reference values by 0.06-0.20%. Excellent linear correlation (R = 0.9997) was obtained between corrected carbon isotope amount ratios and expected carbon isotope amount ratios of the four chosen NIST RMs. The method has proved to be linear within this range (from (13)C/(12)C = 0.010659 to (13)C/(12)C =0.011601), and therefore, it is suitable for the measurement of carbon isotope amount ratios within the natural range of variation of organic carbon compounds, carbonates, elemental carbon, carbon monoxide, and carbon dioxide. In addition, a CO2 gas sample previously characterized in-house by conventional dual inlet isotope ratio mass spectrometry has been analyzed and excellent agreement has been found between the carbon isotope amount ratio value measured by MC-ICPMS and the IRMS measurements. Absolute values for carbon isotope amount ratios traceable to the SI are given for each NIST RM, and the combined uncertainty budget (including instrumental error and each parameter contributing to Russell expression for mass bias correction) has been found to be < 0.1% for the four materials. The advantage of the method versus conventional gas source isotope ratio mass spectrometry measurements is that carbon isotope amount ratios are measured as C(+) instead of CO2(+), and therefore, an oxygen (17)O correction due to the presence of (12)C(17)O(16)O(+) is not required. Organic compounds in solution can be measured without previous derivatization, combustion steps, or both, thus making the process simple. The novel methodology opens new avenues for the measurement of absolute carbon isotope amount ratios in a wide range of samples.     

A technique for the determination of 18O/16O and 17O/16O isotopic ratios in water from small liquid and solid samples

We have developed a new technique in which a solid reagent, cobalt(III) fluoride, is used to prepare oxygen gas for isotope ratio measurement from water derived either from direct injection or from the pyrolysis of solid samples. The technique uses continuous flow, isotope ratio monitoring, gas chromatography/mass spectrometry (irmGC/MS) to measure the delta18O and delta17O of the oxygen gas. Water from appropriate samples is evolved by a procedure of stepped pyrolysis (0-1000 degrees C, typically in 50 degrees C increments) under a flowing stream of helium carrier gas. The method has considerable advantages over others used for water analysis in that it is quick; requires only small samples, typically 1-50 mg of whole rock samples (corresponding to approximately 0.2 micromol of H2O); and the reagent is easy and safe to handle. Reproducibility in isotope ratio measurement obtained from pyrolysis of samples of a terrestrial solid standard are delta18O +/- 0.54, delta17O +/- 0.33, and delta17O +/- 0.10/1000, 1sigma in all cases. The technique was developed primarily for the analysis of meteorites, and the efficiency of the method is illustrated herein by results from water standards, solid reference materials, and a sample of the Murchison CM2 meteorite.     

High-precision continuous-flow measurement of delta13C and deltaD of atmospheric CH4

We describe our development of a CH4 preconcentration system for use with continuous-flow gas chromatograph combustion isotope ratio mass spectrometry (GC/C/IRMS). Precision of measurement of delta13C-CH4 is 0.05/1000 (1sigma) on multiple 60-mL aliquots of the same ambient air sample. The same front-end on-line CH4 preconcentration system allows us to measure deltaD of CH4 by gas chromatography IRMS when the combustion furnace is replaced with a pyrolysis oven (GC/P/IRMS). Precision of measurement for deltaD-CH4 is 1.5/1000 (1sigma) using 120 mL of ambient air based on multiple aliquots of the same air sample. These are the first reported measurements of atmospheric CH4 using GC/P/IRMS methodology. Each isotope analysis can be made much more rapidly (30-40 min) than they could using off-line combustion of an air sample (1-6 h) followed by conventional dual-inlet IRMS measurements (12-20 min), while requiring much less total volume and retaining a comparable level of precision and accuracy. To illustrate the capabilities of our preconcentration GC/C/IRMS system, we compare the results of measurement of 24 background air samples made using both GC/C/IRMS and conventional vacuum line/dual-inlet IRMS methodology. The air samples were collected on a shipboard air sampling transect made across the Pacific Ocean in July 2000 and are part of an ongoing atmospheric CH4 research program. The average difference between the two methods of IRMS analyses on these 24 samples is 0.01 +/- 0.03/1000 (95% confidence interval) for delta3C-CH4. These are the first measurements to be reported of air samples directly intercompared for delta13C-CH4 using both GC/C/IRMS and dual-inlet IRMS measurement methodology. Measurement of deltaD-CH4 of these air samples is also presented as an illustration of the ability of this system to resolve small isotopic differences in remote air. High-precision measurement of delta13C and deltaD of atmospheric CH4 made using our coupled preconcentration GC/IRMS system will greatly improve our ability to utilize isotopic data in understanding spatial and temporal changes in atmospheric CH4 and the biogeochemistry of its sources and sinks.     

Measurement of sulfur isotope compositions by tunable laser spectroscopy of SO2

Sulfur isotope measurements offer comprehensive information on the origin and history of natural materials. Tunable laser spectroscopy is a powerful analytical technique for isotope analysis that has proven itself readily adaptable for in situ terrestrial and planetary measurements. Measurements of delta(34)S in SO2 were made using tunable laser spectroscopy of combusted gas samples from six sulfur-bearing solids with delta(34)S ranging from -34 to +22 per thousand (also measured with mass spectrometry). Standard deviation between laser and mass spectrometer measurements was 3.7 per thousand for sample sizes of 200 +/- 75 nmol SO(2). Although SO(2)(g) decreased 9% over 15 min upon entrainment in the analysis cell from wall uptake, observed fractionation was insignificant (+0.2 +/- 0.6 per thousand). We also describe a strong, distinct (33)SO(2) rovibrational transition in the same spectral region, which may enable simultaneous delta(34)S and Delta(33)S measurements.     

Evaluation of gas chromatographic isotope fractionation and process contamination by carbon in compound-specific radiocarbon analysis

The relevance of both modern and fossil carbon contamination as well as isotope fractionation during preparative gas chromatography for compound-specific radiocarbon analysis (CSRA) was evaluated. Two independent laboratories investigated the influence of modern carbon contamination in the sample cleanup procedure and preparative capillary gas chromatography (pcGC) of a radiocarbon-dead 3,3',4,4',5,5'-hexachlorobiphenyl (PCB 169) reference. The isolated samples were analyzed for their 14C/12C ratio by accelerator mass spectrometry. Sample Delta14C values of -996 +/- 20 and -985 +/- 20 per thousand agreed with a Delta14C of -995 +/- 20 per thousand for the unprocessed PCB 169, suggesting that no significant contamination by nonfossil carbon was introduced during the sample preparation process at either laboratory. A reference compound containing a modern 14C/12C ratio (vanillin) was employed to evaluate process contamination from fossil C. No negative bias due to fossil C was observed (sample Delta14C value of 165 +/- 20 per thousand agreed with Delta14C of 155 +/- 12 per thousand for the unprocessed vanillin). The extent of isotopic fractionation that can be induced during pcGC was evaluated by partially collecting the vanillin model compound of modern 14C/12C abundance. A significant change in the delta13C and delta14C values was observed when only parts of the eluting peak were collected (delta13C values ranged from -15.75 to -49.91 per thousand and delta14C values from -82.4 to +4.71 per thousand). Delta14C values, which are normalized to a delta13C of -25 per thousand, did not deviate significantly (-58.9 to -5.8 per thousand, considering the uncertainty of approximately +/-20 per thousand). This means that normalization of radiocarbon results to a delta13C of -25 per thousand, normally performed to remove effects of environmental isotope fractionation on 14C-based age determinations, also cor-rects sufficiently for putative isotopic fractionation that may occur during pcGC isolation of individual compounds for CSRA.     

Conversion of carbon into CF4 for SI-traceable measurements of absolute carbon isotope amount ratios: a feasibility study

The feasibility of performing SI-traceable carbon isotope amount ratio measurements following conversion of carbon into CF4 was studied. A procedure for the direct fluorination of carbon with elemental fluorine was developed, and the conversion step was checked for losses, blank contributions, and the absence of systematic isotope effects. Gas chromatography was used to identify and quantify the gaseous fluorination products and to isolate CF4 from byproducts. After fluorination of graphite carbon, CF4 and perfluoroalkanes with up to six carbon atoms were observed as reaction products. Within an uncertainty of 10%, the graphite carbon was fully recovered in the gaseous carbon fluorides, with the main product being CF4 (80-90%) and C2F6 as the major byproduct. The fluorination and GC procedures were found to introduce an alteration not bigger than 0.03 +/- 0.04/1000 on the isotopic composition of CF4. Carbon blank contributions introduced during the fluorination procedure were below 0.5% relative to a typical sample of 4 mg of carbon. For two of the materials investigated, the carbon isotope ratios measured on a differential mass spectrometer were reproducible within a standard deviation of approximately 0.1/1000 for several individual fluorinations. For these materials, the developed fluorination procedure is a straightforward process, which can be used as a foundation to establish SI-traceable measurements of carbon isotope amount ratios. However, for the third graphite material the formation of byproducts (C2F6-C6F14) was found to induce significant isotopic fractionation.     

High sensitivity tracer detection using high-precision gas chromatography-combustion isotope ratio mass spectrometry and highly enriched [U-13C]-labeled precursors.

The use of highly enriched, uniformly labeled fatty acid ([U-13C]) with analysis by high-precision gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS) has been evaluated as a metabolic tracer technique. 13C/12C ratios are routinely determined to precisions (SD) of less than 0.00001 (delta PDB less than 1/1000) for greater than 10 ng of fatty acid, and less than 0.001 (delta PDB less than 100/1000) for samples of 30 pg of fatty acid, the latter corresponding to a 100-fmol sample. Baseline fatty acid 13C/12C in human plasma fractions is shown to fluctuate not more than 0.000 04 (delta PDB 4/1000) over 10 h. 13C/12C enrichments greater than 0.001 (delta PDB 100/1000) are obtained in a fatty acid plasma fraction subsequent to a 10-mg dose of 42% 13C-labeled stearic acid to a 78-kg adult. Biokinetics are discerned over an 13C/12C enrichment range of less than 0.0002 (approximately 13/1000 in delta PDB units) in plasma. A means for correction of isotope ratio contamination due to carbon-containing derivatives is presented. High-precision GCC-IRMS used in concert with highly enriched tracers is shown to possess advantages versus organic GC/MS for stable isotopic tracer detection and is superior to radiotracer methods in terms of dose sizes and analysis efficiency.     

Generation of O2 from BaSO4 using a CO2-laser fluorination system for simultaneous analysis of delta18O and delta17O

With the observation of mass-independent isotopic anomalies in numerous atmospheric molecules, the ability to measure both delta17O and delta18O in a range of samples is needed. Sulfate oxygen isotopic studies conventionally report only delta18O values. Recent findings indicate that sulfate delta17O and delta18O values, particularly the delta17O value (= delta17O - (0.52)(delta18O)), can provide independent information on the origin, mixing, and transformation of sulfate in the atmospheric and surface environments, which is not resolvable by only delta18O measurements. Existing methods for analyzing sulfate delta17O and delta18O are extremely laborious and demand high-purity BrF5. Here we report a novel method of generating O2 directly from Barite (BaSO4) for simultaneous analysis of delta18O and delta17O by isotope ratio mass spectrometry (IRMS). The method utilizes a CO2-laser fluorination system that can also be used to quantitatively generate O2 from silicates and oxides. Partial but consistent oxygen yields from BaSO4 are obtained for samples >4 mg. Correction factors of +9.4% for delta18O and 4.89% for delta17O are obtained, and there is no deviation in the delta17O value due to the nonquantitative O2 generation. The system may process more than a dozen samples per working day, with analytical error of +/-0.05% and +/-0.8% for delta17O and delta18O, respectively. This new method is ideal for studies emphasizing an accurate sulfate delta17O value.     

Precision trace gas analysis by FT-IR spectroscopy. 2. The 13C/12C isotope ratio of CO2

We report the development of a method of carbon stable isotope ratio analysis based on 1-cm-1 resolution Fourier transform infrared (FT-IR) spectroscopy, deployable in both laboratory and field applications. We demonstrate the determination of the 13C/12C ratio of CO2 (i.e., delta 13CO2) in air with an analytical precision of the order of +/- 0.1/1000 (i.e., +/- 0.01%). The FT-IR method relies on calibration using synthetically calculated absorbance spectra and a multivariate calibration algorithm. The method requires no sample preparation other than optional drying of the sample and may be applied directly to ambient air samples containing approximately 350 mumol mol-1 CO2 (molar mixing ratio). It may also be applied to samples more concentrated in CO2, such as human breath, approximately 5% CO2. We demonstrate the utility of the technique to the analysis of delta 13CO2 in air during an experimental field campaign and to the laboratory-based analysis of human breath. A similar method could also be used to determine the H/D ratio in atmospheric water vapor.     

High-precision laser spectroscopy D/H and 18O/16O measurements of microliter natural water samples

Newly available gas analyzers based on off-axis integrated cavity output spectroscopy (OA-ICOS) lasers have been advocated as an alternative to conventional isotope-ratio mass spectrometers (IRMS) for the stable isotopic analysis of water samples. In the case of H2O, OA-ICOS is attractive because it has comparatively low capital and maintenance costs, the instrument is small and field laboratory portable, and provides simultaneous D/H and 16O/18O ratio measurements directly on H2O molecules with no conversion of H2O to H2, CO, or H2/CO2-water equilibration required. Here we present a detailed assessment of the performance of a liquid-water isotope analyzer, including instrument precision, estimates of sample memory and sample mass effects, and instrumental drift. We provide a recommended analysis procedure to achieve optimum results using OA-ICOS. Our results show that, by using a systematic sample analysis and data normalization procedure routine, measurement accuracies of +/-0.8 per thousand for deltaD and +/-0.1 per thousand delta18O are achievable on nanoliter water samples. This is equivalent or better than current IRMS-based methods and at a comparable sample throughput rate.     

Chlorine isotope analysis of submicromole organochlorine samples by sealed tube combustion and thermal ionization mass spectrometry

Improved sensitivity in the analysis of stable chlorine isotopes of organochlorines (delta(37)Cl-OCl) has been established using sealed tube combustion in conjunction with thermal ionization mass spectrometry (TIMS). TIMS of chlorine isotopes was performed on <85 nmol of Cl with an achievable precision of <0.25 per thousand for pure inorganic chloride samples and 0.46 per thousand for chloride liberated from organochlorines (OCls). This makes possible significant reductions in the overall sample size requirement, as compared to the techniques of gas source stable isotope ratio mass spectrometry (SIRMS). Yields in excess of 99% were demonstrated in the dechlorination of <0.14 micromol 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT), and the overall yield, including purification of liberated chloride, was 86-97%. The accuracy of TIMS in the measurement of chlorine isotopes derived from OCls was confirmed by analysis of a DDT sample previously analyzed with SIRMS.(9) Using the described method for TIMS, the DDT sample gave a bulk chlorine isotope ratio of delta(37)Cl -4.42 +/- 0.46 per thousand (1sigma). The reported value from SIRMS analysis is -4.34 +/- 0.25 per thousand, indicating the conformity of the two methods.     

Determination of 234U/238U ratio: comparison of multi-collector ICPMS and ICP-QMS for water, hair and nails samples, and comparison with alpha-spectrometry for water samples

The (234)U/(238)U ratio in water, hair and nails samples was determined by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) and inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) and by alpha-spectrometry for the water samples only. A correlation of 0.99 was found between the two ICPMS methods and of 0.98 with alpha-spectrometry. The range of activity ratios was between 0.9 and 2.6 according to the MC-ICPMS measurements. The reproducibility of both ICPMS techniques was better than 4% for water samples containing 1 mug l(-1) of uranium and a (234)U/(238)U atom ratio of 54.9 x 10(-6). Sample preparation for the ICPMS consisted of dilution of water samples containing >10 microg l(-1) of uranium and measurement time was approximately 1 min, while alpha-spectrometry involved pre-concentration and separation of the uranium and counting times of 1,000 min.     

Sulfur isotope analysis of sulfide and sulfate minerals by continuous flow-isotope ratio mass spectrometry

A continuous flow method (CF-IRMS) for the rapid determination of the sulfur isotope composition of sulfide and sulfate minerals has significant advantages over the classic extraction method in terms of the reduced sample quantity and a rapid analytical cycle of less than 8 min/ analysis. For optimum performance, the technique is sensitive to a number of operating parameters, including sample weight and the O2 saturation of the Cu-reduction reactor. Raw data are corrected using a calibration based on five international and internal standards ranging from -17.3 to +20.3 per thousand, which requires monitoring in order to correct the effect of changing delta18O of the sample gas on the measured mass 66 values. Measured sulfur contents are within 1-1.5% of expected values and the reproducibility of delta34S values is +/-0.1 per thousand (1sigma). The technique has been used successfully for more than 1000 analyses of geological samples with a wide range of delta34S from -20 to +20 per thousand.     

Observations of large mass-independent fractionation occurring in MC-ICPMS: implications for determination of accurate isotope amount ratios

Multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) suffers large bias in isotope amount ratio determinations which has to be properly accounted for. The choice of the proper discrimination model is crucial. Over the last few decades, the exponential mass-bias correction model (Russell's law) has become a standard curriculum in isotope amount ratio measurements. In nature, however, isotopic fractionation that deviates significantly from the exponential model has been known for a long time. Recently, such fractionation was also observed in MC-ICPMS. This phenomenon is termed mass-independent fractionation. In this study, significant departure from the mass-dependent fractionation model is reported for germanium and lead with the most dramatic occurring for germanium-73 and lead-204 isotopes wherein, on average, close to a half percent bias was evidenced from the Russell's law.     

Analytical developments for high-precision measurements of W isotopes in iron meteorites

A procedure was developed to accurately measure the W isotopic compositions of iron meteorites with a precision of better than +/-0.1 epsilon on epsilon182W and epsilon184W (normalized to 186W/183W). Purification of W was achieved through a two-step, ion-exchange procedure. In most cases, the yield is better than 80%, and purified W solutions are clear of matrix elements and direct isobars of W. The final W solutions were analyzed using a Micromass Isoprobe multicollector inductively coupled plasma mass spectrometer (MC-ICPMS). Tests performed on mixtures of terrestrial standards and meteorite samples demonstrate that the method is accurate and that epsilon182W variations as small as approximately 0.1 epsilon can be detected. Analyses of three different aliquots of the Gibeon (IVA) iron meteorite obtained over a period of 6 months show identical epsilon182W values with a weighted mean of 3.38 +/- 0.05, consistent with literature data for IVA iron meteorites, and indicating that the metal-silicate differentiation event in its parent body was either contemporaneous with or slightly postdated (by up to approximately 2.5 My) the formation of refractory inclusions. We demonstrate our ability to measure epsilon184W accurately and precisely (within +/-0.1 epsilon), which is useful for characterizing cosmogenic and nucleosynthetic effects that may be present in iron meteorites. We also report for the first time measurements of epsilon180W, albeit with large error bars (<+/-4 epsilon, in most cases).